Pentachlorocyclopentene-3-one-2-yl phosphonates and insecticidal use thereof



PENTACHLOROCYCLOPENTENE 3 ONE 2 YL PHOSPHONATES AN INSECTICIDAL USE THEREOF Sidney B. Richter, Chicago,Ill., assignor to Velsicol Chemical Corporation, Chicago, 111., a corporation of Illinois No Drawing. Application March 14, 1957 Serial No. 645,926

' 10 Claims. 01. 167-30) This invention relates to new compositions of matter. In particular it relates to phosphonates of pentachlorocyclopentenone and pentachlorocyclopentenethione.

One object of the present invention is the preparation of new halogenated phosphonates.

Another object of the present invention is the preparation of new agricultural chemicals, particularly insecticides and miticides.

Still another object of the present invention is the preparation of new compositions containing the pentahaloeyclopentenone or pentahalocyclopentenethione configuration.

.The compositions of the present invention include the compounds of the following structure:

wherein each -X is independently selected from the group consisting of chlorine and bromine; Y is selected from thegroup consisting of sulfur and oxygen; and each R isindependently selected from the group consisting of aliphatic, cycloaliphatic, and aryl radicals. In many instances the compositions of structure I wherein R is as previously defined and contains from 1 to 14 carbon atoms are preferred.

Of particular interest are the compositions of the above structure where X is chlorine, Y is oxygen and R is a lower alkylor alkenyl radical. The radical represented by R in structure I can contain halogen atoms or other desirable substituents such as sulfur, oxygen and the like. Most interesting compounds are those wherein R of structure I contains from one to three halogen atoms.

The compositions of the present invention are prepared by the reaction of 2,3,4,4,5,5-hexachloro-2-cyclo pentenone or 2,3,4,4,5,5hexachloro-2-cyclopentenethione and a tertiary ester of phosphorous acid (hereinafter referred to as a triphosphite) chosen in accordance with the identity of R in structure I, that is the R groups being introduced into the product as part of the triphosphite reactant. This reaction is quite unexpected in view of the literature which shows the formation of phosphates and not phosphonates by the reaction of specific carbonyl compounds such as chloral containing halogen atoms in the position alpha to the carbonyl radical and a triphosphite as previously defined.

On the basis of this past work, it would appear that the present compositions could not beprepared by the direct reaction of a phosphite and a carbonyl compound containing an alpha halogen atom.

'2,3,4,4,5,5-hexachloro-2-cyclopentenone, one of the reactants of the process of the present invention has been known to the art for over fifty years and is discussed by Newcomer and McBee in 71 J.A.C.S. 946, the latter de- United States Patent 2 scribing its preparation from octachlorocyclopentene by the action of concentrated sulfuric acid. Similarly, the triphosphites are not new compounds, their preparation being reported in the literature.

The reaction of the present invention can be performed under atmospheric pressure or below or above atmospheric. Temperatures in the range of.0100 C.- are operable, although it is preferred to perform the reaction at temperatures between 025 C. This reaction can be efliciently run as a batch or a continuous process The time of the reaction will depend on many factors such as the exact reaction temperature, equipment design, exact identity of reactants, contact area, and the like. While solvent is not required for the process of the present invention, organic solvents such as benzene, xylene can be used. Also, excess quantities of the reactant can be utilized as solvent.

Since the reaction is an equimolar reaction, the ratio of reactants should be approximately 1:1. However, as previously indicated, the process may be performed with an excess of either reactant.

The phosphites used in the present process are trisubstituted, that is, they contain three aliphatic, aryl or cycloaliphatic radicals attached to the three oxygen atoms of the phosphite configuration. They may con-, tain one aryl group and two aliphatic radicals or other like combinations. Likewise, they may be substituted with halogen, oxygen, or other like groups. The following table illustrates the triphosphite reactants of the present invention and the product of its reaction in accordance with the present invention. However, this list is only for purpose of illustrating the present invention and should not be construed as a limitation thereon.

TABLE I Product of Reaction Product of Reaction Trlphosphite with 2,3,4,4,5,5 hexwith 2,3,4,4,5,5 hexachloro 2 cycloachloro 2 cyclopentenone pentenethione trlmethyl 0,0 dlmcthyl 1,3,4; 0,0 dimethyl 1,3,4,

5,5 pentachlorocy- 5,5 pentachlorocyclopentene 3 one clopentene 3 thlone 2 yl phosphonate. 2 yl phosphonate. trlethyl 0,0 -diethyl -1,3,4,5,5- 0,0 dlethyl 1,3,4,5,5- pentachlorocyclopeupentachlorocyclopentene-3-one-2-yl tcne-B-thlone-Z-yl phosphonate. phosphonate.

trl(eh1orobutyl) 0,0 dl(ehlorobutyl) 1,3,4,5,5 pentachlorocyclopentene 3 one 2 yl phosphonate.

trlisooctyl 0,0 diisooetyl 1,3,4,

5,5 pentaehloroeyclopentene 3 one 2 yl phosphonate.

0,0 di(chlorobutyl) 1,3,4,5,5 pentachlorocyclopentene 3 -v thione 2 yl phosphonate.

0,0 dilsooctyl 1,3,4, 5.5 pentachlorocycltr pentene 3 thlone 2 yl phosphonate.

trlisopropyl- 0,0 diisopropylnitrile- 0,0 diisopropylnitrilenitrile. 1,3,4,5,5 pentachloro- 1,3,4,5,5 pentachloroeyclopentene 3 one cyclopentene 3 thi- 2 yl phosphonate. one 2 yl phosphonate tri(1-methyl-1- 0,0 di(1 methyl 1 0,0 di(1 methyl l carboethoxycarbo ethoxy mecarbo ethoxy memethyl). thyl) 1,3,4,5,5 penthyl) 1,3,4,5,5 pen tachloroeyelopentene tachlorocyclopentene 3 one 2 yl phospho- 3 thione 2 yl phosnate. phonate. tri 1-(N.N- 0,0 di [1-(N.N.dibutyl 0,0 di [1-(N.N-dibutyl dibutyl carbnmyl) methyl] carbamyl) 1,3,4,5,5 pentachloro methyl]. cyclopentene 3 one 2 yl phosphonate. ttlmenthyl 0,0 dimenthyl 1,3,4,

5,5 pentachlorocyclopentene- 3 one 2 yl phosphonate.

earbamyl) methyl] 1,3,4,5,5 pentaehloro cyclopentene 3 thione- 2 yl phosphonate.

0,0 dlmenthyl 1,3,4,

5,5 pentaehloroeyclopentene 3 thtone 2- yl phosphonate.

When a phosphite reactant containing dissimilar radicals attached to its three oxygen atoms is utilized in the present process there can be prepared a mixture of the phosphonates of the present invention. This mixture may be used without separation of its components or the phosphonates can be separated by distillation or other like methods. When the isomer of 2,3,4,4,5,5- hexaohloro-2-cyclopentenone, namely 2,3,4,4,5,5-hexachloro-3-cyclopentenone, is reacted with a tri-substituted phosphite in accordance with the present invention, there is produced new, valuable phosphorous-containing organic compositions likewise containing the pentachlorocyclopentene configuration.

The following examples illustrate the preparation of the new compositions of the present invention, but should not be construed as imposing limitations on the present invention:

Example I PREPARATION OF 0.0-DIETHYL-1,3,4,5,5-PENTACHLO- ROCYCLOPENTENE-3-ONE-2-YL PHOSPHONATE 2,3,4,4,5,5-hexachloro-2-cyclopentenone (43.5 grams; 0.15 mol) was placed in a three-necked glass reaction vessel equipped with addition funnel, reflux condenser, thermometer and stirrer, and containing benzene (150 ml.). The solution was cooled to 2 C. by means of an ice water bath. Triethyl phosphite (24.0 grams; 0.15 mol) in benzene (100 ml.) was added slowly from the addition funnel. The addition time was 1 /2 hours during which time the temperature of the reaction mixture was maintained between about 2-5 C. The reaction solution was then refluxed for 1 /2 hours, at the end of which time the solvent and unreacted reactants were removed under reduced pressure. The desired product was recovered by distillation of the residue as the cut with a boiling point of 152-160 C. at 0.77 mm. Hg pressure. p

The chlorinecontent was analyzed and found to' be 46.01% as compared to a theoretical chlorine content of 45.41% for C H Cl O P. The structure of the product was confirmed by infraredanalysis which showed the presence of a carbonyl group.

Example II OF 0,0-DI-(CHLOROMETHYL)4,3,33,5-

' PHO S PREPARATION PENTACHLOROCYCLOPENTENEs-ONE 2 YL PHONATE 2,3,4,4,5,5-hexachloro-2-cyclopentenone (28.9 grams;

0.10 mol) is placed in a three-necked glass reaction vessel equipped with thermometer, stirrer, reflux condenser and addition funnel, and containing benzene (150 ml.). The solution is cooled to about 2 C. by an icewater bath and tri-(chloromethyl) phosphite (22.9

grams: 0.10 mol) in benzene 100 ml.) is added thereto from the addition tunnel in a I la-hour addition time during which time the temperature of the reaction mixture is maintained at about 2-5 C. Then the reaction mixture isrefluxed for approximately 1 /2 hours and solvent and remaining starting material is removed under reduced pressure. The product is then purified from the residue.

' Example III PREPARATION OF 0,0CATECHOLI,3,4,5,5*PENTACHLO- ROCYCLOPENTENE-3-ONE-2-YL PHOSPHONATE 2,3,4,4,5,S-hexachloro-Z-cyclopentenone (23.9 grams;

0.10 mol) is placed in a three-necked glass reaction vessel equipped with thermometer, stirrer, reflux condenser, and

stirrer, and containing benzene (150 ml.). The solution is cooled to about 2 C. by an ice-water bath and di- (catechol)beta chloro ethyl phosphite (21.9 grams; 0.10

mol) in benzene (100 ml.) is added thereto from the addition funnel in a l /a-hour period during which time the temperature is maintained at about 25 C. Then the reaction mixture is refluxed for approximately 1 /2 hours at which time solvent and unreacted starting material is removed under reduced pressure. Product is then purified from the residue.

As previously indicated, the compositions of the present invention are highly useful in the control of insects, mites, and other undesirable plant pests. These compounds provide superior protection against numerous pests which prevent or inhibit the growth of valuable plants. Indicative of these valuable properties of the present compounds are the following results from tests performed with the compositions of the present invention in the control of said plant pests.

In the first test, 0,0-l-diethyl-1,3,4,5,5-pentachlorocyclopentene-3-one-2-yl phosphonate was tested against the Mexican bean beetle. The test compound was formulated into a 10% by weight wettable powder which was dispersed in a quantity of water necessary for a final concentration 0.4% by weight of the actual test compound. Cranberry bean plants were dipped in this dispersion and dried. Subsequently untreated Mexican bean beetles were placed thereon for 48 hours. At the end of this time the percent mortality of the beetles was showing the high toxicity of the compound of the present invention.

A second test was performed to confirm the above indicated high insecticidal toxicity of these new com pounds. In these tests the test insect was the pea aphid. 0,0 diethyl-1,3,4,5 ,5 -penta'chlorocyclopentene-3-one-2-yl phosphonate was formulated into a 10% by weight wettable powder and dispersed in water to prepare a dispersion containing 0.4% by weight actual test compound. This dispersion was sprayed onto caged pea aphids by spraying at 20 pounds pressure for approximately five seconds. The treated insects were then removed from the cage and caged on untreated Windsor broad bean plants. Forty-eight hours after the above treatment the percent mortality of the pea aphids was 100%, verifying the high insecticidal toxicity of these compounds.

Many compounds which are good insecticides are not capable of controlling mites, a most destrictive group of plant pests. In order to determine the miticidal activity of the present compounds, the following test was performed against the greenhouse red spider. 0,0-di ethyl-1,3,4,5,5-pentachlorocyclopentene-3-one-2-yl phosphonate was formulated into a 10% by weight wettable powder and dispersed in water at a concentration of 0.4% by weight of the phosphonate. Red spider intested cranberry bean plants were dipped in this dispersion. Seventy-two hours after this treatment the mortality of the spiders was 100 percent.

Thus it can be said that the new compositions of the present invention are superior insecticides and miticides.

These new compounds can be applied to the material, plants, or area needing protection from injurious crop pests by any of the means known to the art for the application of insecticides and miticides. They can be used in their pure form; they can be formulated with inert carriers, stickers, dispersion agents, wetting agents, and the like; they can be dissolved in organic solvents such as kerosene, benzene, etc.; they can be utilized in conjunction with other pest control agents; or they can be used in other forms known to the art. Examples of formulations of the compositions of the present invention which are readily usable are as follows. In these ensuing examples the term phosphonate of present invention means any one phosphonate of the present inven tion or combinations thereof.

Example IV Percent by weight Phosphonate of present invention 50 Celite 209 50 Celite 209 is a diatomaceous earth utilized as a relatively inert carrier. This formulation may be ground into a dust or granular. It is of value in treatment of seeds, freshly seeded land and young crops.

2,914,439 5 6 Example V I claim:

Percent by weight 1. Phosphonate of present invention 70 7 C1 Micro-Gel s 27 p 0 Triton X-100 3 5 0 e1 i (0a Micro-Cel 800 is a synthetic, relatively inert, porous C1 carrier material consisting substantially of calcium silicate. l Triton X-100 is a Wct'tifl agent chemically an alkyl, aryl polyether alcohol. Thisformulation is a 70% Wettable Wherem R s a radlcal selected from the group cons1st1ng owder suitable for Slum e treatment of unsubst1tuted alkyl, chloroalkyl, cyanoalkyl, carbethp y yp oxyalkyl, and N,N-dibutyl carbamyl alkyl containing from 1 to 14 carbon atoms. E 1 VI 6 Percent by weight 2. O,O-d1(chloromethyl) -1,3,4,5,s pentachlorocyclo- Phos hon t of gs nt nvention pentene 3-o'ne-2-.y1 p p g s g i f 23 3. 0,0-d1ethy1 1,3,4,5,5 pentachlorocyclopentene-3- Isopropyl alcohol 1O (lea-Y1 phfsphonate- Atlas 64690 7 4. O,O-d1methyl 1,3,4,5,5 pentachlorocyclopentene- 3-one-2-yl-phosphonate. Atlas 6-1690 is a commercially obtainable emulsifier 2O g pentachlomcyclopenteneessentially a nonyl-phenol-ethylene oxide detergent. 0 5 5 4 5 h This formulation is an emulsifiable concentrate. g i 'pentac lorocyclo' These examples illustrate formulations in which the 2 g osp f? present compounds can be used, but their use is not he 0 of a hug Insect and i pests limited to use therein. As previously indicated, these 25 Whlch p mes h appdcanon of alethal quanmy of the novel compounds can be used in any of the means known g fi calm te 1 t th f H k to the art, and thus the above illustrations do not limit n p 0 S8 c mg p i grow a ac their application by llloBCtS and mites which comprlses exposing said mate- '1' he actual application of these compounds to the area Hal to an effectly? quanmy the composlmili of or material being protected can likewise be carried out 1 if i F the camposmon of clam by the methods known to this art, such as by spraying, i 2 2 d St f t d dusting, dipping, and the like, selecting the most suit- 6 8 i e F lonuo an g; able formulation by the desired method of application. pes i g Des S 0 a at In addition to the aforementioned utility of the new quan 1 y o e c p n o 6 mm compositions of the present invention as pest control agents, they also have other valuable uses, such as lube oil additives, antifoaming agents, plasticizers, stabilizers, antistatic agents, hydraulic fluid additives, textile conditioners, and the like.

References Cited in the file of this patent UNITED STATES PATENTS UNITED STATES PATENT OFFICE I CERTIFICATE OF CORRECTION- Patent No. 2,914,439 November 24, 1959 Sidney B. Richter It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column 3, line 45, Example II, in the heading, for

"-l,3,3,4,5-" read l,3,4,5,5- column 4, line 39, for "destrictive" read destructive column 6, lines 5 to 7, for that portion of the formula reading -P(OR) read P(OR) Signed and sealed this 12th day of July 1960.

(SEAL) Attest:

KARL H. AXLINE ROBERT C. WATSON Attesting Officgr Commissioner of Patents 

7. THE METHOD OF CONTROLLING INSECT AND MITE PESTS WHICH COMPRISES THE APPLICATION OF A LETHAL QUANTITY OF THE COMPOSITION OF CLAIM
 1. 